Aluminum containing complexes of hexamethylene tetramine



ALUMINUM CONTAINING COMPLEXES OF HEXAMETHYLENE TETRAMINE Filed Feb. 211962 2 Sheets-Sheet 1 Fig. 2 F

L a L G. REBAUDO May 5, 1964 ALUMINUM CONTAINING COMPLEXES OFHEXAMETHYLENE TETRAMINE' 2 Sheets-Sheet 2 Filed Feb. 21, 1962 NM NQ ofpreparing these complexes which comprises reacting a and filled withnitrogen. monoethyl aluminum dissolved in 30 cc. of toluene were UnitedStates PatentOfi 3,132,141 Patented May 1964 ice This invention relatesto aluminium-containing complexes and to methods of preparing them.

I have found that hexamethylene tetramine forms complexes with compoundscontaining the I AlO grouping, to give stable products, the propertiesof which, particularly as polymerization catalysts, are far superior tothose of the corresponding non-complexed alkyl-alurninums.

According to the present invention, therefore, I provide a complexhaving the formula:

in which: a is a number between 1 and 3, R is an alkyl radicalcontaining less than 7 carbon atoms, X is a halogen atom, and n is awhole number selected from 1, 2 and 3.

Further according to the invention we provide a method hexamethylenetetramine. with an alkyl-aluminum or a halogenated alkyl-aluminumderivative, the alkyl group or groups of said derivative containing lessthan 7 carbon atoms. In this method it is preferred that the relativemolar proportions of the reactants should be substantially 1 to 2. Theprocess is advantageously carried out at or near room temperature. 1

Preferred methods of preparing complexes according to the invention aregiven below by way of example:

Example 1 H2) s 4- 2 5 a 6.12 g. (i.e. 43.4 l0- mols) of hexamethylenetetramine, purified by crystallization from ethyl alcohol, and 40 cc. oftoluene which had been dried on the absence of air were introduced intoa flask provided with an agitator 94X mols of dichlorothen added, dropby drop, to the hexamethylene tetramine at atmospheric pressure and roomtemperature.

Initially the reaction was exothermic but for completion requiredheating to about 50 C. for minutes. A

white powder was precipitated, filtered under nitrogen, washed threetimes with heptane and dried at a pressure of 10" mm. Hg. A yield of 13g. of complex was ob- 1 tained. 6 g. of this complex was recrystallizedfrom tolu- 1 ene and, after filtration and drying, yielded 4.2 g. of a jcrystalline compound.

The complex thus obtained was analysed by determining the variousconstituents in the following manner. The aluminum was determined as A10 the chlorine by the Carpentier-Volhard method, the nitrogen with anitrometer, and the carbon and the hydrogen in a combustion furnace.

For the formula given above, the theoretical composition is:

' Percent Al 13.69 Cl 35.99 N 14.22 3C 30.48 H 5.63

In various samples, the following compositions were obtained:

Example 2 (CH N .2A1(C H C1 15 g. (i.e. 0.12 mol) of mouochlorodiethylaluminum were reacted with 7.05 g. (i.e. 0.05 mol) of hexamethylenetetramine purified by recrystallization from ethyl alcohol, in 30 cc. ofn-heptane at atmopsheric pressure and room temperature. A yield of 15.5g. of complex was obtained, crystallized in the same manner as describedin Example 1 and a similar analysis was carried out.

composition is:

. Percent Al 14.17 Cl 18.63 C 44.09 H 8.39 N 14.69

In various samples, the following compositions were obtained:

Al 14. 03 13. 92 1a. 94 01 1s. 20 18.30 18. 10 N- 14. so 14. 42 14. 70 o44. 11 44. 35 41. H 8.36 s. 41 8.32

T1118 complex 1s solid at room temperature. It is stable when protectedfrom air and humidity and only begins to decompose, at 10* mm. Hg, aboveC. It is partially soluble in toluene, more so when hot than cold, andis only slightly soluble in aliphatic hydrocarbons.

FIGURE 2 of the accompanying drawings shows the X-ray diifractionpattern of the complex thus prepared, which proves its crystallinity.

Example 3 2) 6N4-2A1(C2H5)3 dual pressure of 0.1 mm. Hg); the reactionproduct had a boiling point of 206 C.

The same complex was obtained when the process was carried out in asolvent medium and at a lower temperature, and also with differentproportions of the starting materials.

Analysis of the product confirmed the formula given above. At roomtemperature, the product is a colorless For the formula (CH N.2Al(C H Clthe theoretical Example4 V I 194 cc. (i.e. 0.086 mol) of triisobutylaluminum and 6.75 g. (i.e. 0.048 mol) of hexamethylene tetramine,purified by crystallization from ethanol, were reacted in 50 cc. ofcyclohexane. .The initial reaction at room temperature was exothermic,there being immediate dissolution of the hexamethylene tetrarnine, thenon being heated to 40 C. and after 30 minutes, 7 g. of a white powderwere precipitated, the analysis of which confirmed it had thecomposition of the formula stated above.

The same precipitate was formed when different proportions of the twostarting materials were used.

The complex thus obtained is solid at room temperature; it is stable inthe absence of air and humidity and is partially soluble in toluene,more so when hot than when cold, and is only slightly soluble inaliphatic hydrocar bons.

FIGURE 3 of the accompanying drawings shows the X-ray diffractionpattern of the complex thus prepared, which proves its crystallinity.

In each of these examples of preparation, an excess of one or the otherof the reactants was used and it was found that the "complex obtainedand isolated in each 021156 was always of the same composition. As hasbeen seen,

all the complexes are stable products which can easily be prepared andisolated. The above experiments were carried out with various solventsand the same complexes were obtained irrespective of the dilution of.the reactants used.

Complexes according to the invention can also be prepared -by using,instead of the alkyl-aluminum or halogenated alkyl-aluminum derivativesthemselves, products which enable them to be obtained. 7

The complexes according to the invention are particularly useful aspolymerization catalysts, either alone for polymerization andco-polymerization of aldehydes, or in combination with a co-catalyst forthe polymerization and co-polyrnerization of alpha-olefins. In theseapplications they "are more efiective than the correspondingnon-complexed alkyl-aluminum compounds, particularly when polymerizationis eficcted at temperature below 0 C.

What is claimed is:

1. A substance of the formula in which a. is a number between 1 and 3,

R is an alkyl of 1-6 carbon atoms,

X is a halogen atom, and

n is a whole number selected from 1, 2 and -3.

2. The substance of the formula (CH N .2AlC H Cl 3. The substance of theformula (CH N .2Al (C H C1 4. The substance of the formula (CH N .2Al(CH 3 5. The substance of the formula v 2)s 4- 4 9)3 References Cited inthe file of this patent UNITED STATES PATENTS (1913 Series) OTHERREFERENCES Smolin et al.: S-Triazine and Derivatives, Interscience Pub.Inc., New York, 1959, p. 555.

Bonitz: Chemische Berichte, vol. 88, pp. 74275 1, 1955.

1. A SUBSTANCE OF THE FORMULA